Photographic material incorporating a phosphoric acid ester of a polyoxyalkylene compound



United States Patent PHOTOGRAPHIC MATERIAL INCORPORATING A PHOSPI-IORIC ACID ESTER OF A POLYOXYAL- KYLENE COMPOUND Jozef Frans Willems, Wilrijk-Antwerp, Joseph Louis De Munck, Beveren-Waas, and Robrecht .l'ulius Thiers, Brasschaat, Belgium, assignors to Gevaert Photo-Producten N.V., Mortsel-Antwerp, Belgium, a company of Belgium No Drawing. Filed Dec. 21, 1962, Ser. No. 246,357 Claims priority, application Belgium, Dec. 22, 1961,

41,244, Patent 611,864 9 Claims. (Cl. 96-107) This invention relates to an improved photographic material and more especially to silver halide emulsion layers having a better developability and an increased general light-sensitivity.

It is known to further increase the general sensitivity of photographic emulsions, which already may be optimally sensitized for the whole range of the spectrum with the so-called chemical sensitizers, e.g, the sulfur sensitizers, by adding polyglycols to the photographic elements (see British patent specifications 548,019 and 600,058).

It is also known that the same increase of sensitivity may be obtained when incorporating into the photographic material alkylene oxide polymers prepared by the polymerization of alkylene oxide in the presence of dehydration products of hexitol rings, aliphatic alcohols, aliphatic acids, amines, amides and phenols (see British patent specifications 592,676, 748,745 and 748,750).

Further, it is known that these polyglycols and alkylene oxide polymers must have a molecular weight of at least 400 and that it is practically necessary to use compounds having a molecular weight from 1500 to 2000 and more to obtain a substantial effect.

Contrary to the other known methods to increase the sensitivity of silver halide emulsions, e.g., the methods according to which the inherent sensitivity is increased by chemical sensitizers, and the methods according to which the spectral absorption is increased by cyanine dyestuffs, it has been observed that the final sensitivity of the silver halide emulsion layers containing the above described compounds is higher, as these compounds have a favorable influence upon the development of these silver halide emulsion layers in the conventional developers. Thus these compounds may 'be considered as developing accelerators.

However, it is also known that these compounds may be used as ingredients in more sensitive silver halide emulsion layers, but they impair the keeping quality of these layers, particularly at high temperatures and elevated degrees of relative humidity, since they induce a substantial increase of fog. It has also been observed that the incorporation of these compounds into the photographic material in order to prepare more sensitive silver halide emulsion layers impaired the image tone of the developed silver, thereby forming brown and red-brown images.

It has now been found that the developa'bility of the light-sensitive emulsions can be favorably influenced by adding to at least one emulsion layer or other layer comprised by the photographic element, a phosphoric acid ice ester of a polycxyalkylene compound as hereinafter described, said polyoxy-alkylene compound showing substantially less action on itself.

On applying this new method, it was found that with these new compounds higher sensitivities can be obtained than with the starting polyoxyalkylene compounds, and also that these new compounds give rise to less fog on storage. Furthermore when using these new compounds, the image tone of the developed silver remains unaltered.

The new developing activators are phosphoric acid esters of a polyoxyalkylene compound corresponding to one of the following general formulae:

and

wherein:

R is an alkylene group of from about 2 to about 3 carbon atoms, preferably an ethylene group,

n is a positive integer from 5 to 35,

R is a member selected from the group consisting of an alkyl radical containing from about 1 to about 20 carbon atoms, preferably of at least 15 carbon atoms, and an aralkyl radical,

R is a member selected from the group consisting of an aryl radical such as a phenyl radical, an alkylaryl radical, such as a nonylphenyl radical and a hydrogen atom,

R is an alkyl radical containing from about 1 to about 20 carbon atoms, and

X is an acid radical.

The phosphoric acid esters used according to the invention increase the relative sensitivity and particularly the gamma of the photographic material. The polyoxyalkylene compounds used for preparing said phosphoric acid esters may be prepared by polymerization of ethylene oxide or by reaction of ethylene oxide with an alcohol, a phenol, a glycol, an amine, an amide or an acid.

The amount of said phosphoric acid ester yielding a very good developing activation without any substantial fog increase is between 30 mg. and 6 g. per mole of silver halide of the emulsion layer to be developed.

Among the phosphoric acid esters, the monoesters and the diesters as well as the triesters of phosphoric acid are included. However, the triesters of phosphoric acid or mixtures of diesters and triesters of phosphoric acid are preferably used.

Preferably, for the purpose of the invention the polyethylene oxide derivatives are used; but there may be also used polyalkylene oxide derivatives of the same type,

R is a member selected from the group consisting of an alkyl radical, containing from about 1 to about 20 carbon atoms and an aralkyl radical,

R is a member selected from the group consisting of an aryl radical such as a phenyl radical, and an alkylaryl radical, such as nonylphenyl radical and a hydrogen atom,

R is an alkyl radical containing from about 1 to about 20 carbon atoms,

X- is an acid radical, and

n is a positive integer from 5 to 35.

By way of illustration, some preparations of products or developing activators used according to the invention are given hereinafter.

The phosphoric acid esters can also be prepared by reesterification of a lower phosphoric acid alkyl ester with one of the polyoxyalkylene compounds mentioned above.

PREPARATION 1 A mixture of 50 g. (0.056 mole) of p-nonylphenoxytetradecaethylenoxy-ethanol of the following structure:

1.34 g. (0.009 mole) of phosphorus pentoxide and 100 cm. of ether is refluxed for two hours on a water-bath. The formed residue is filtered OE and the filtrate is evaporated. According to analysis, the viscous residue consists of 23.6% of mono(p-nonylphenoxy-tetradecaethylenoxy-ethyl) phosphate, 10.4% of di(p-nonylphenoxytetradecaethylenoxy-ethyl)phosphate and 66% of tri(pnonylphenoxy-tetradecaethylenoxy-ethyl)phosphate.

PREPARATION 2 A mixture of g. (0.4 mole) of octadecanoyl-tetraethylenoxy-ethanol of the structure:

CI7H35(I%O (CHFCHFO)4CHTCHQOH 0.943 g. (0.006 mole) of phosphorus pentoxide and 50 cm. of ether is refluxed for 2 hours. The formed residue is filtered off and the filtrate is evaporated. According to analysis, the viscous residue consists of 10.1% of di(octadecanoyl tetraethylenoxy ethyl)ph0 sphate and 89.9% of trioctadecanoyl tetraethylenoxy ethyl) phosphate.

4 PREPARATION 3 A mixture of 200 g. (0.096 mole) of polyoxyethylene glycol having an average molecular weiht of 2000, 2.32 g. (0.016 mole) of phosphorus pentoxide and 500 cm. of benzene is refluxed for 2 hours. The solution is filtered and the filtrate is evaporated under vacuum. The residue consists of the phosphoric acid triester of the above polyethylene glycol.

PREPARATION 4 A mixture of g. (0.03 mole) of polyoxyethylene glycol having an average molecular weight of 4000, 0.76 g. (0.005 mole) of phosphorus pentoxide and 250 cm. of benzene is refluxed for 2 hours. The solution is filtered and the filtrate is evaporated under vacuum. The residue consists practically entirely of the phosphoric acid triester of the above polyoxyethylene glycol.

PREPARATION 5 A mixture of 122 g. of Mulgofen O (trade name for a condensation product of a polyoxyalkylene glycol with a higher alphatic alcohol, sold by Antara Chemicals, a Division of General Aniline & Film Corporation, New York, N.Y., U.S.A.), 4 g. (0.028 mole) of phosphorus pentoxide and 25 0 cm. of benzene is refluxed for 2 hours. The solution is filtered and the filtrate is evaporated under vacuum. The residue consists practically entirely of the phosphoric acid triester of the above polyoxyalkylenc glycol.

PREPARATION 6 A mixture of 120 g. of Scurol S (trade name for a polyoxyalkylene derivative of the following structure:

Alkyl sold by the Socit des Usines Chirniques Rhdne- Poulenc, Paris, France), 4.7 g. (0.033 mole) of phosphorous pentoxide and 250 cm. of benzene is refluxed for 2 hours. The solution is filtered and the filtrate is evaporated. The residue consists practically entirely of the phosphoric acid triester of the above polyoxyalkylene derivative.

PREPARATION 7 A mixture of 27 g. of a polyoxyethylene derivative having the following structure:

wherein x+y=50, 0.5 g. (0.0035 mole) of phosphorus pentoxide and 125 om. of benzene is refluxed for two hours on a water-bath. The formed residue is filtered off and the filtrate is evaporated under vacuum. Titration shows that the residue did not consist entirely of the phosphoric acid triester of the above polyoxyethylene derivative, but that it contained still 0.76 milliequivalent of the phosphoric acid diester of this derivative per gram of residue.

PREPARATION 8 Mixture of 72 g. of a polyoxyethylene derivative of the following structure:

17 sa H 2 z- )w 0.71 g. (0.006 mole) of phosphorus pentoxide and 250 cm. of benzene is refluxed for 2 hours on a Water-bath. The for-med residue is filtered off and the filtrate is evaporated under vacuum. Titration shows that the residue did not consist entirely of the phosphoric acid triester of the above polyoxyethylene derivative, but that it contained still 0.06 milli-equivalent of the phosphoric acid diester of this derivative per gram of residue.

PREPARATION 9 A mixture of 127 g. of a polyethylene oxide derivative of the following structure:

(CHz-CHg-O);H

RCN

ll 0 0H,0Hz0 ,-H wherein x+y=50, and

' R represents the alkyl radicals present in the coconut fat in the following ratios: C H -about 8% C H about C H about 49% C H about 18% C H about 9% C 7H353.bOut C H about 2.4 g. (0.017 mole) of phosphorus pentoxide and 250 cm. of benzene is refluxed for 2 hours on a water-bath. The formed residue is filtered off and the filtrate is evaporated under vacuum. Titration shows that the residue did not consist entirely of the phosphoric acid triester of the above polyethylene oxide derivative, but that it contained still 0.3 milliequivalent of the phosphoric acid diester of this derivative per gram of residue.

PREPARATION The following mixture is refluxed for 4 hours: 60 g. of a polyethylene oxide derivative of the following structure:

wherein x+y= and R represents a stearyl group, 3 g. of phosphorus pentoxide and 500 cm. of anhydrous benzene. The formed residue is filtered off and the filtrate is vacuum-evaporated. The residue is dried over paraffin. Titration shows that the residue consists entirely of the phosphoric acid triester of the above polyethylene oxide derivative.

Preferably, the developing activators used in the present invention are added directly to the silver halide emulsion. However, they may also be added to one or several layers forming a water-permeable element with the emulsion layer, e.g., a hydrophilic colloid layer adjacent to said emulsion layer. The addition of these compounds may eventually be effected in the form of an aqueous solution or of a mixture of water and an organic solvent which does not impair the photographic properties of the light-sensitive material.

A solution of the developing activators may eventually be coated on the emulsion layer.

The developing activators used in the present invention may be incorporated at different steps of the emulsion preparation. For instance, they may be added as a separate addition or in admixture with one or several other ingredients used for the initial precipitation of the silver halide grains, during the physical or chemical ripening process or in any other step before coating the emulsion. However, they are preferably added to the emulsion after its chemical ripening and just before coatmg.

The optimum amount added to the emulsion depends upon the selected compound, the nature of the colloidal binding agent for the silver halide grains and the amount and the nature of the silver halide present in the emulsion. Generally, the developing activators used in the present invention are added in an amount of from 30 mg. to 6 g. per mole of silver halide. If necessary, these compounds, however, may still be added in amounts beyond these values.

In order to increase the light-sensitivity of a silver halide emulsion layer of a photographic material the developing activators used in the present invention can be incorporated into the silver halide emulsion layer in combination with small amounts of a sulfur containing compound, such as allyl isothiocyanate, allyl thiourea and sodium thiosulfate, small amounts of reduction sensitizers, such as the tin compounds described in the Belgian patent specifications 493,464 and 568,687 and the iminoaminomethane sulfinic acid compounds described in the British patent specification 789,823, or small amounts of precious metal compounds, such as of gold, platinum, palladium, iridium, ruthenium and rhodium. Of course, the sensitizing effect of the compounds initially present in the gelatin may be very advantageously completed by the new developing activators.

In combination with the developing activators used in I the present invention, stabilizers may also be used, e.g., mercury compounds, and the compounds mentioned in the prior art and claimed in the Belgian patent specifications 571,916 and 571,917. It is also usual to sensitize and/or to stabilize silver halide emulsions by incorporating cadmium salts or by processing these emulsions in the presence of cadmium salts. In addition, other ingredients, such as fog inhibiting agents, color couplers, developing substances, hardeners and wetting agents, may also be added in a known manner to the emulsion, without impairing it in any way.

Owing to their property of promoting the developability, the new compounds may be very efficiently used to increase the X-ray sensitivity and the general lightsensitivity of orthochromatic, panchromatic and all special emulsions as Well as the conventional non spectrally sensitized emulsions. They may be added separately or in combination with optically sensitizing dyestuffs. In the latter case, the addition must be effected before or after the addition of the optically sensitizing dyestuffs. In addition, they may be very advantageously used in the most various emulsions, since they lead to an outstanding sensitivity increase in the negative as well as in the positive emulsion types.

The following examples point out very clearly that the addition of the phosphoric acid esters according to the invention to a light-sensitive silver halide emulsion induces a higher relative sensitivity and gamma for a fog remaining practically the same.

Example 7 shows that the use of phosphoric acid esters induces a higher light-sensitivity and less fog than when using the known polyoxyalkylenes or the polyoxyalkylene derivatives which are used to prepare the phosphoric acid esters according to the invention.

Example 1 A washed negative coarse-grained gelatin silver bromoiodide emulsion (average grain size: 0.8 in which the silver halide consists of 94.5 mole percent of silver bromide and 5.5 mole percent of silver iodide, is ripened until the optimum light-sensitivity is obtained. After the addition of a panchromatic sensitizing dyestulf and other usual ingredients, the emulsion is coated on a support (sample 1).

Other samples are prepared'by adding every time to determined amounts of the same emulsion before coating, the hereafter indicated amounts of developing accelerators per mole of silver halide present. Then, they are processed in the same manner as sample 1. After drying and exposure, the samples are developed for 7 minutes at 20 C. in a solution having the following composition:

Water cm. 800 Monomethyl-p-aminophenol sulfate g 2 Hydroquinone g 5 Sodium sulfite(anhydrous) g Borax g 10 Boric acid g 5 Potassium bromide g 0.5 Water to cm. 1000 SENSITOMETRICAL RESULTS 8 Example 4 The emulsion has the same composition as that desa-mple Added wmpolmdin $011016 Relative Gamma Fog scribed in Example 1 but the average grain size of the of silver halide sensitivity silver halide grams amounts to 1,41. and the silver halide 1 100 33 0 07 consists of 96 mole percent of silver bromide and 4 mole 2 0.034 g. of the compound ao- 135 1 percent of silver iodide. The emulsion samples contain cording to preparation 1. 3 0.34 g. of the compound w 162 Q38 0 08 the hereafter indicated amounts of developmg acceler cording to preparation 1. ators: 4 3.40 gd of the compound ac- 178 0.42 0. 08 5 0.511.1 5 11522 552231 O. 3., 0. o sample Adda i a ese Gamma Fog cording to preparation of silver hahde sensitivity 6 0.34 g(.1 01 the compound 210- 282 0.48 0.10

cor ing 0 prepara ion 6.

1 100 0. 41 0. 00 7 'i miiii io gig ifigfi io. 224 2 1.70 g. ofthe compound ac- 170 0.48 0. 00

cording to preparation 1. 3 0.34 g. of the compound 210- 182 0. 50 0. 09 cording to preparation 3. Example 2 4 0.34 g. of the compound oc 246 0. 52 0.10

cording to preparation 4. After the addition of the hereafter indicated amounts 5 gfa g fi gggggffig f 282 of developing accelerators and a processing identical to 0 1.70 gdlof the com ound 210- 224 0.52 0.00

- cor 'ng to preparation 5. that of Example 1, the following sensitometric results 7 340 g the compound w 230 (L54 MO are obtained: cording to preparation 5.

8 0.050 g. of the compound ac- 182 0. 44 0. 09

cording to preparation 6. Sample Added ofomlpourgd g./rnole Relative Gamma Fog 9 l j g i g 5 93 3 353;- 234 50 10 51m a sensltmty 10 1.70 g. of the compound ac 234 0.55 0.10

cording to preparation 7. 1 100 0,34 0.08 11 3.40 gd o1 rm compound a70- 257 0.55 0.10

.034 i th (1 1 ,3 cor ing 0 preparation 2 0 ai to iiggtggfi 18 0 5 0 09 12 1.70 g. of the compound ac- 204 0. 52 0. 09 3 0.31 g. of the com ound ac- 100 0. 44 0.11 cording to preparation cording to preparation 7. 13 3.40 g. of the compound ae- 200 0.55 0. 09 4 3.40 g. of the compound ac- 224 0. 50 0. 11 wrdmg to preparation cording to preparation 7 14 1.70 g. 01 the compound 210- 219 0. 53 0.10 5 0.034 g. of the compound ac- 123 0. 35 0. 00 wrdmg to preparatmn cording to preparation 8. 15 3.40 g. of the compound a(: 230 0.53 0.10 6 0.34 g. of the compound ac- 162 0. 41 0. 10 cording 130 Preparation ,7 3 fgrdinfgtifilo preparatioln 8. 24

g. o ecompoun ac- 2 0.50 0.13

ggoidingf 2% preparation1 8. 13 3 Example 5 0. g. o e compoun ac- 2 0. 7 0.10 cording to preparation The following sensitometric results are obtalned as de 0.34 g. or the compound ac- 200 0,47 0,11 scribed in Example 1, but after havmg developed the cording to preparation 9. o 340 0mm compound am 229 0 52 M2 samples for 7 minutes at 20 C. 1n a solution having the cording to preparation 9. followin g composition:

Monomethyl-p-aminophenol sulfate g 2 Example 3 0 Sodium sulfitc (anhydrous) g 100 Hydroquinone g 4 After the addition of the hereafter indicated amounts of Sodium tetraboram 10 aq 2 developing accelerators and a processing identical to that Water 3 1000 After 35 hours of incubation at 57 C. and 34% relative Added compound in g.lmole 01 Relative humidity Sample silver halide sensitivity Gamma Fog Relative Gamma Fog sensitivity 1 100 0. 60 0.14 0.55 0.14 2 0.340 g. of the compound according to 135 0. 76 0.15 0.60 0.15

preparation 7. 100 0.68 0.14 100 0.65 0.17 4. 0.340 g. of the compound according to 123 0.78 0.18 141 0. 72 0.19

preparation 3. 5- 100 0.80 0.12 100 0.82 0.13 6- 132 1.06 0.13 132 0.98 0.15

preparation 7. 7 3.40 g. of the compound according to 138 1.05 0.15 1.12 0.17

preparation 5.

of Example 1, the following sensitometric results are ob- Example 6 tained:

Sample Added compound in gJmole Relative Gamma Fog of silver halide sensitivity 1 100 0. 35 0. 09 2 0.34 g. of the compound ac- 126 0.35 0. 11

cording to preparation 3. 3 0.34 g. of the compound 210- 195 0. 45 0.12

cording to preparation 3. 4 0.034 g. of the compound 510- 0.39 0. 12

cording to preparation 4. 5 0.34 g. of the compound aa- 224 0.46 0.15

cording to preparation 4. 6 0.034 g; of the compound 110- 117 0. 37 0. l0

cording to preparation 5. 7 0.34 g. of the compound ac 186 0.42 0. 11

' cording to preparation 5.

A washed negative coarse-grained gelatin silver bromoiodine emulsion, in which the silver halide consists of 98.2 mole percent of silver bromide and 1.8 mole percent of silver iodine, is ripened at 42 C. After addition of 630 mg. per mole silver halide of 5-methyl-7-oXy-s-triazolo- [1,5-o1] pyrimidine as a stabilizer and other usual ingredients, the emulsion is coated on a support (Sample 1).

Other samples are prepared by adding every time to determine amounts of the same emulsion before coating, the hereafter indicated amounts of developing accelerators per mole of silver halide present. They are then processed in the same manner as Sample 1.

After drying and exposure, the samples are developed for 4 minutes in a solution having the following compositi OH Rr-N Water cm. 800

(R 'O)n H Monomethyl-p-ammophenol sulfate g 4 Sodium sulfite (anhydrous) g 65 5 Hydroquinone g 10 )n Sodium carbonate (anhydrous) g 45 fi and Potassium bromide g ll R R-O H O R-O H Water to cm. 1000 3 After 36 hours of incubation at 57 C. and 34% relative Added compound in g./mole of Relative humidity Sample silver halide sensitivity Gamma Fog Relative Gamma Fog sensitivity 1 '100 2.80 0. 06 112 2. 30 0. 2 2 g. of the compound according to 112 3. 0.07 117 2. 74 0.09

preparation 1. 3 2 g. of the compound according to 135 3.18 0.07 129 2.69 0.11

preparation 2. 4 2 g. of the compound according to 162 3.47 0.08 152 2.69 0.19

preparation 3. 5 2 g. of the compound according to 148 3.62 0.06 155 2. 90 0.12

preparation 4. 6 2 g. of the compound according to 148 3.71 0.06 151 3.12 0.10

preparation 5. 7 2 g. of the compound according to 148 3.72 0.06 151 2.72 0.09

preparation 6. 8 2 g. of the compound according to 155 3.35 0.06 158 2.41 0.09

preparation 7. 9 2 g. of the compound according to 151 3.29 0.07 151 2. 90 0.12

preparation 8. 10 2 g. of the compound according to 151 3.55 0.06 138 3.89 0.13

, preparation 9.

Example 7 wherein:

After addition of the hereafter indicated amounts of developing accelerators and a processing identical to that R is an alkylene group of from about 2 to about 3 carbon atoms,

of Example 6, the following sensitometric results are n lsaposltlvemteger fmmsto R is a member selected from the group consisting of an obtained:

After 36 hours of incubation at 57 C. and 34% relative Added compound in gJmole of Relative humidity Sample silver halide sensitivity Gamma Fog Relative Gamma Fog sensitivity 2 2 g. of the compound according to 151 3.29 0.07 151 2. 90 0.12

preparation 8.

3 2 g. of the starting polyoxyethylene 138 2.90 0.07 2.48 0.30

compound of preparation 8.

4 2 g. of the compound according to 170 4.59 0.06 189 3.13 0.14

preparation 4.

5 2 g. of polyoxyethylene glycol (aver- 141 3.45 0.09 145 2.61 0.18

age molecular weight: 4,000).

6 2 g. of the compound according to 162 3.47 0.08 151 2.69 0.19

preparation 3.

7 1.6 g. of polyoxyethylene glycol (aver- 135 3.42 0. 08 135 2.62 0.19

age molecular weight: 200).

8 3 g. of polyoxyethylene glycol (aver- 141 3.40 0.08 135 2.60 0.28

age molecular weight: 200).

9 2 g. of the compound according to 135 3.18 0.07 129 2.69 0.11

preparation 2.

10 2 g. of the starting polyoxyethylene 100 2.90 0. 06 100 2. 0. 06

compound of preparation 2.

11 2 g. of the compound according to 112 3.20 0.07 117 2.74 0.09

preparation 1.

12 2 g. of the starting polyoxyethylene 100 2.90 0.06 105 2. 60 0.07

compound of preparation 1.

alkyl radical containing from about 1 to about 20 carbon atoms, and an aralkyl radical,

13 is a member selected from the group consisting of a hydrogen atom, an aryl radical and an alkylaryl radical, R is an alkyl radical containing from about 1 to about 20 carbon atoms, and X is an acid radical.

2. A light-sensitive photographic material comprising a support and at least one gelatino silver halide emulsion layer containing a phosphoric acid ester of a polyoxyalkylene compound in an amount between 30 mg. to 6 g. per mole of silver halide said phosphoric acid ester being a condensation product of a phosphorus compound selected from the group consisting of phosphorus pentoxide and phosphorus oxychloride with a polyoxyethylene compound corresponding to one of the following general formulae:

R1-0 F FO)n H o oH oHron-H wherein:

R is a member selected from the group consisting of an alkyl radical, containing from about 1 to about 20 carbon atoms and an aralkyl radical,

R is a member selected from the group consisting of an aryl radical, an alkylaryl radical, and an hydrogen atom,

R is an alkyl radical containing from about 1 to about 20 carbon atoms,

X- is an acid radical, and

n is a positive integer from 5 to 35.

3. The light-sensitive photographic material of claim 1 wherein the phosphoric acid ester of a polyoxyalkylene compound is the diester.

4. The light-sensitive photographic material of claim 1 wherein the phosphoric acid ester of a polyoxyalkylene compound is the triester.

5. The light-sensitive photographic material of claim 1 wherein the phosphoric acid ester of a polyoxyalkylene compound is the phosphoric acid triester of the compound:

wherein n has a value of about 50.

6. The light-sensitive photographic material of claim 1 wherein the phosphoric acid ester of a polyoxyalkylene compound is the phosphoric acid diester of:

wherein x+y=50.

7. The light-sensitive photographic material of claim 1 wherein the phosphoric acid ester of a polyoxyalkylene compound is the phosphoric acid diester of the polyoxyethylene derivative having the structure:

8. The light-sensitive photographic material of claim 1 wherein the phosphoric acid ester of a polyoxyaikylene compound is the phosphoric acid diester of a polyethylene oxide derivative having the formula:

wherein x+y=50 and R represents a mixture of alkyl radicals of from C7H15 to C H 9. The light-sensitive photographic material of claim 1 wherein the phosphoric acid ester of a polyoxyalkylene compound has the structure:

References Cited by the Examiner UNITED STATES PATENTS NORMAN G. TORCHIN, Primary Examiner. 

1. A LIGHT-SENSITIVE PHOTOGRAPHIC MATDRIAL COMPRISING A SUPPORT AND AT LEAST ON E GELATINO SILVER HALIDE EMULSION LAYER CONTAINING A PHOSPHORIC ACID ESTER OF A POLOXYALKYLENE COMPOUND IN AN AMOUNT BETWEEN 30 MB. TO 6G. PER MOLE SILVER HALIDE SAID PHOSPHORIC ACID ESTER OF A POLYOXYALKYLENE COMPOUND BEING AN ESTER OF PHOSPHORIC ACID AND A POLYOXYALKYLENE COMPOUND CORRESPONDING TO ONE OF THE FOLLOWING GENERAL FORMULAE: 